EP1043340A1 - Procédé de production de polymère de chlorure de vinyl - Google Patents

Procédé de production de polymère de chlorure de vinyl Download PDF

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Publication number
EP1043340A1
EP1043340A1 EP00104108A EP00104108A EP1043340A1 EP 1043340 A1 EP1043340 A1 EP 1043340A1 EP 00104108 A EP00104108 A EP 00104108A EP 00104108 A EP00104108 A EP 00104108A EP 1043340 A1 EP1043340 A1 EP 1043340A1
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EP
European Patent Office
Prior art keywords
polymerization
vinyl chloride
antioxidant
added
weight
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00104108A
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German (de)
English (en)
Inventor
Makoto c/o Enbi Gijutsu Kenkyusho Ooura
Tadashi C/O Enbi Gijutsu Kenkyusho Amano
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Shin Etsu Chemical Co Ltd
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Shin Etsu Chemical Co Ltd
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Publication of EP1043340A1 publication Critical patent/EP1043340A1/fr
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
    • C08F14/02—Monomers containing chlorine
    • C08F14/04—Monomers containing two carbon atoms
    • C08F14/06—Vinyl chloride
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates

Definitions

  • This invention relates to a process for producing a vinyl chloride polymer. More particularly, it relates to a vinyl chloride polymer production process by which vinyl chloride polymers having less uneven plasticizer absorption and having good anti-initial discoloration properties and thermal stability can be produced stably.
  • an antioxidant is conventionally added for the purpose of improving anti-initial discoloration and thermal stability of the vinyl chloride polymers to be obtained and also for keeping polymerization conversion constant and making uneven plasticizer absorption less occur.
  • it is added, e.g., before the polymerization is initiated, during polymerization, at the time the internal pressure has dropped at the last stage of polymerization, or before, during or after the recovery of remaining unreacted monomers.
  • the antioxidant has a polymerization inhibitory action, it is usually added to a polymerization mixture at the last stage of polymerization also for the purpose of terminating the polymerization. Since, however, antioxidants are usually in the form of powder, it is difficult to press the antioxidant into a polymerization vessel at a constant rate when the inside of the vessel stands pressurized at the last stage of polymerization.
  • a method in which an antioxidant is pressed into the polymerization vessel by means of a pump after the antioxidant has been dissolved in an organic solvent such as methanol and toluene and (2) a method in which a powdery antioxidant is dispersed in an aqueous medium by the aid of a suspending agent or an emulsifying agent to form an aqueous antioxidant dispersion, which is then added by means of a pump.
  • a plunger pump and a diaphragm pump are described (Japanese Laying-open Publication No. 60-149608).
  • the method (1) enables its addition at a constant rate and without any problem even when the inside of the vessel stands pressurized.
  • the organic solvent used to dissolve the antioxidant is included in an effluent emitted out of the polymerization vessel after the polymerization, bringing about the problem of an increase in COD in the effluent.
  • the organic solvent used may cause problems that it mixes into the resultant vinyl chloride polymer to cause an odor of the product and an odor at the time of processing it or that it mixes into monomers recovered when unreacted monomers are collected.
  • some antioxidants have a low solubility in organic solvents, where the organic solvents must be used in a large quantity to make the above problems more serious.
  • the method (2) can solve these problems.
  • a pump such as a plunger pump or a diaphragm pump when the polymerization vessel is held at an internal pressure of 0.3 to 1.2 MPa at the last stage of polymerization
  • the pump must have a pump-out pressure higher than the polymerization pressure, requiring a great mechanical energy. Because of such a great mechanical energy, particles contained in the aqueous antioxidant dispersion tend to break or aggregate in the pump at its ball check valve and so forth to which the mechanical energy is most applied especially when the dispersion is being fed.
  • the method (2) has such a great problem. This may seriously occur especially when the pump has a high pump-out pressure, and may cause a great difficulty when the antioxidant dispersion is press-added into the polymerization vessel when its inside stands pressurized at the last stage of polymerization.
  • an object of the present invention is to provide a vinyl chloride polymer production process that enables addition of the aqueous antioxidant dispersion at a constant rate and stably, without causing any block-up of the interior of the pump even when the polymerization vessel is held at a high internal pressure.
  • the present invention provides a process for producing a vinyl chloride polymer, the process comprising the steps of:
  • vinyl chloride or a monomer mixture containing vinyl chloride is polymerized in a polymerization vessel in the presence of a polymerization initiator and a dispersant, in an aqueous medium and by a conventional method.
  • the monomer material to be polymerized is a vinyl chloride monomer or a monomer mixture containing vinyl chloride.
  • the monomer mixture is a mixture of at least 50% by weight of vinyl chloride with a monomer copolymerizable with the vinyl chloride.
  • the copolymerizable monomer may include, e.g., vinyl esters such as vinyl acetate and vinyl propionate; acrylates such as methyl acrylate and ethyl acrylate, or methacrylates; olefins such as ethylene and propylene; maleic anhydride; acrylonitrile; styrene; and vinylidene chloride. Any of these may be used alone or in combination of two or more types.
  • dispersant usable in the polymerization step may be any of those conventionally used in the production of vinyl chloride polymers.
  • This dispersant may include, e.g., water-soluble cellulose ethers such as methyl cellulose, hydroxyethyl cellulose, hydroxypropyl cellulose, hydroxypropyl methyl cellulose; water-soluble polymers such as water-soluble partially saponified polyvinyl alcohol, acrylic acid polymers and gelatin; oil-soluble emulsifiers such as sorbitan monolaurate, sorbitan trioleate, glycerol tristearate and an ethylene oxide-propylene oxide block copolymer; and water-soluble emulsifiers such as polyoxyethylene sorbitan monolaurate, polyoxyethylene glycerol oleate and sodium laurate. Any of these may be used alone or in combination of two or more types.
  • the dispersant may usually be used in an amount of from 0.02 to 0.2 part by weight based on 100 parts by weight of the monomer.
  • This polymerization initiator may be any of those conventionally used in the production of vinyl chloride polymers.
  • This polymerization initiator may include, e.g., percarbonates such as diisopropyl peroxydicarbonate, di-2-ethylhexyl peroxydicarbonate and diethoxyethyl peroxydicarbonate; perester compounds such as t-butyl peroxypivarate, t-hexyl peroxypivarate, t-butyl peroxyneodecanoate and ⁇ -cumyl peroxyneodecanoate; peroxides such as acetylcyclohexyl sulfonyl peroxide, 2,4,4-trimethylpentyl-2-peroxyphenoxyacetate and 3,5,5-trimethylhexanoyl peroxide; azo compounds such as azobis-2,4-dimethylvalerontrile and azobis(4-methoxy-2,
  • the polymerization initiator may usually be used in an amount of from 0.01 to 0.3 part by weight based on 100 parts by weight of the monomer.
  • aqueous medium deionized water is usually used.
  • the aqueous medium in the polymerization step may usually be used in an amount of from 1.0 to 3.0 parts by weight based on 100 parts by weight of the monomer.
  • polymerization it is suitable for the polymerization to be carried out at a temperature ranging from 30 to 75°C.
  • the process of the present invention is characterized by this step of adding the antioxidant.
  • a dispersion prepared by dispersing the antioxidant in an aqueous medium is added by means of a uniaxial eccentric screw pump.
  • the antioxidant used here may be any of oil-soluble antioxidants commonly used in the production of vinyl chloride polymers.
  • This antioxidant may include, e.g., phenolic compounds such as 2,2-di(4'-hydroxyphenyl)propane, hydroquinone, p-methoxyphenol, t-butylhydroxyanisole, n-octadecyl-3-(4-hydroxy-3,5-di-t-butylphenyl)propionate, 2,5-di-t-butylhydroquinone, 4,4-butylidene-bis(3-methyl-6-t-butylphenol), 3,5-di-t-butyl-4-hydroxytoluene, 2,2'-methylene-bis(4-ethyl-6-t-butylphenol), triethylene glycol bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl) propionate], pentaerythritol tetrakis[3-(3,
  • the antioxidant is uniformly and stably dispersed in the aqueous medium by the aid of a suspending agent and optionally an emulsifying agent, and is used in the form of an aqueous dispersion.
  • the suspending agent used here may include water-soluble partially saponified polyvinyl alcohol, water-soluble cellulose derivatives (e.g., hydroxypropyl methyl cellulose and hydroxyethyl methyl cellulose), gelatin, fatty acid partial esters of polyhydric alcohols (e.g., glycerol monostearate and sorbitol monolaurate), and polyoxyethyl esters of polyhydric alcohols.
  • the emulsifying agent may include anionic emulsifiers which are alkali metal salts, alkaline earth metal or ammonium salts of higher fatty acids (e.g., lauric acid, palmitic acid and stearic acid), paraffinic sulfonic acids, alkyl alcohol sulfates or alkylarylsulfonic acids. Any of these suspending agent and emulsifying agent may be used alone or in combination of two or more types.
  • anionic emulsifiers which are alkali metal salts, alkaline earth metal or ammonium salts of higher fatty acids (e.g., lauric acid, palmitic acid and stearic acid), paraffinic sulfonic acids, alkyl alcohol sulfates or alkylarylsulfonic acids. Any of these suspending agent and emulsifying agent may be used alone or in combination of two or more types.
  • the suspending agent and emulsifying agent may be mixed in a proportion ranging from 10/0 to 3/7, and preferably from 10/0 to 5/5, in a weight ratio of suspending agent/emulsifying agent, since the volume resistivity and anti-initial discoloration of the resulting vinyl chloride polymer are affected at a controlled low level.
  • the antioxidant may preferably have an average particle diameter of from 0.5 to 50 ⁇ m, and more preferably from 1 to 10 ⁇ m. If it has too large a particle diameter, the resultant aqueous dispersion may have a low storage stability, where particles may settle or float to become separated to cause block-up in the pump, tank and piping. If it has too small a particle diameter, the dispersion may have an improved stability, but it takes much time and power to make the particles have a fine particle diameter, resulting in a high cost.
  • the antioxidant in the aqueous dispersion may usually be in a concentration ranging from 10 to 70% by weight, preferably from 20 to 70% by weight, and more preferably from 30 to 60% by weight. If the antioxidant is in too high a concentration, the resultant aqueous dispersion may have a low fluidity. If on the other hand it is in too low a concentration, the aqueous dispersion may have to be added in a large quantity.
  • concentration of the suspending agent in the aqueous antioxidant dispersion there are no particular limitations on the concentration of the suspending agent in the aqueous antioxidant dispersion. In view of improving the state of dispersion of the antioxidant in the aqueous antioxidant dispersion and also keeping the viscosity of the dispersion within an appropriate range, it may preferably be in the range of from 0.01 to 10% by weight.
  • the aqueous antioxidant dispersion may be added before polymerization, during polymerization, particularly at the last stage of polymerization, or before collection, during collection or after collection of remaining unreacted monomers.
  • it may preferably be added at the last stage of polymerization where the internal pressure of the polymerization vessel drops.
  • the present invention can remarkably be effective when it is added at the time the internal pressure of the polymerization vessel has dropped to 0.3 to 1.2 MPa, and preferably 0.3 to 1.0 MPa, at the last stage of polymerization.
  • the aqueous antioxidant dispersion may usually be added in an amount of from 0.0001 to 0.5 part by weight in terms of the antioxidant, based on 100 parts by weight of the vinyl chloride monomer or monomer mixture containing vinyl chloride monomer charged into the polymerization vessel. Especially when it is added at the time the internal pressure of the polymerization vessel has come to 0.3 to 1.2 MPa, it may preferably be added in an amount of from 0.001 to 0.05 part by weight in terms of the antioxidant, in view of advantages that the polymerization reaction can be terminated effectively and vinyl chloride polymers having good anti-initial discoloration properties can be obtained.
  • This uniaxial eccentric screw pump is a pump comprising a internally double-threaded stator (made of an elastic material, having an oblong cross section), and an externally single-threaded rotor (made of a metal, having a round cross section) which is so inserted to the interior of the stator as to be rotatably engaged therewith so that a fluid (aqueous antioxidant dispersion) can be forwarded continuously while rotating the rotor eccentrically in the stator.
  • Fig. 1 shows an example of the uniaxial eccentric screw pump used in the present invention.
  • a stator housing 1 which is cylindrical and made of a metal, an elastic stator 2 made of a synthetic rubber is fixed.
  • an externally threaded rotor 4 (a uniaxial eccentrically single-threaded member made of a metal) is so inserted as to be rotatably engaged with the stator.
  • a drive shaft 6 transmits the rotation of a drive motor 5 to the main body of the pump.
  • Universal joints 7 and 8 also transmit the rotation of the drive motor 5 to the externally threaded rotor 4.
  • a bearing 9 supports the drive shaft 6.
  • the universal joints 7 and 8 are connected through a coupling rod 10.
  • a shaft sealer 12 prevents the fluid from running along the drive shaft 6 to leak outside; the fluid being sucked into the pump casing 11.
  • An end stud 13 forms a discharge outlet 14, and is connected to piping (not shown) through which the fluid discharged out of the discharge outlet is transported.
  • a fluid suction inlet 15 is also formed at the head of the pump casing 11.
  • the rotation of the drive motor 5 is transmitted to the drive shaft 6 and is further transmitted to the externally threaded rotor 4 through the universal joint 7, coupling rod 10 and universal joint 8.
  • This externally threaded rotor 4 rotates on the eccentric shaft center.
  • the externally threaded rotor 4 reciprocates while rotating the interior of the elastic stator 2.
  • the space formed between the externally threaded rotor 4 and the elastic stator 2 is severely sealed along a tangent line formed between the externally threaded rotor 4 and the elastic stator 2.
  • the seal line thus formed continues from the suction side to the discharge side.
  • this uniaxial eccentric screw pump according the antioxidant addition step of the present invention enables prevention of the solid matter that may occur when the conventional plunger pump or diaphragm pump is used. Hence, the interior of the pump can be free from being blocked up with it and the fluid can always be fed at a constant rate. Even if any solid matter has occurred in the pump, the fluid is so forwarded as to be forced out together with the solid matter, and hence the interior of the pump is by no means blocked up.
  • a polymerization modifier, a chain transfer agent, a pH adjuster, a gelation improver, an antistatic agent and so forth which are commonly used in the production of vinyl chloride polymers may optionally appropriately be added to the polymerization mixture before the polymerization is initiated, in the course where the polymerization is carried out or after the polymerization is completed.
  • any antioxidant other than the one described previously may also be added as long as it does not obstruct the effect of the present invention, which may be added before the polymerization is initiated, in the course where the polymerization is carried out or after the polymerization is completed.
  • a polymerization vessel having a internal volume of 2 m 3 and made of stainless steel, 980 kg of deionized water, 382 g of partially saponified polyvinyl alcohol having a degree of saponification of 80.5 mole% and 143 g of hydroxypropyl methyl cellulose having a degree of methoxy-substitution of 28.5% by weight and a degree of hydroxypropoxy-substitution of 8.9% by weight were charged.
  • the inside of the polymerization vessel was evacuated until its internal pressure reaches 60 mmHg, and thereafter 700 kg of vinyl chloride monomer was charged.
  • an aqueous antioxidant dispersion A as shown in Table 1 was press-added into the polymerization vessel for 2 minutes by means of a uniaxial eccentric screw pump (trade name: MOHNO PUMP, the uniaxial eccentric screw pump shown in Fig. 1; manufactured by Heishin Soubi K.K.; Model 6NE-08) at the number of pump revolutions of 140 rpm.
  • the aqueous antioxidant dispersion A added to the polymerization mixture held in the polymerization vessel was in an amount of 420 g as so intended. Unreacted monomers were collected, and the resultant polymer slurry was dehydrated and then dried to obtain a vinyl chloride polymer.
  • the above operation as one batch was repeated by 10 batches.
  • the aqueous antioxidant dispersion on the 10th batch was in an amount of 420 g as so intended, which did not change from that in the 1st batch.
  • the interior of the pump was examined, but any solid matter was not found to have adhered.
  • the plasticizer absorption, anti-initial discoloration properties, thermal stability and bulk density of the vinyl chloride polymer obtained after the 10th-batch operation were measured in the following way and also the value of COD of polymerization effluent flowed out of the production process was measured according to JIS K0102.
  • Example 2 Polymerization was carried out in the same manner as in Example 1 except that the uniaxial eccentric screw pump was replaced with a diaphragm pump (trade name: IS2AZ-02-20DID SP; manufactured by Nikkiso K.K.) and the aqueous antioxidant dispersion A was pressed into the polymerization vessel for 2 minutes under a pump stroke set at 37.8%. The aqueous antioxidant dispersion A added to the polymerization mixture was in an amount of 422 g as so intended. Unreacted monomers were collected, and the resultant polymer slurry was dehydrated and then dried to obtain a vinyl chloride polymer.
  • a diaphragm pump trade name: IS2AZ-02-20DID SP; manufactured by Nikkiso K.K.
  • the plasticizer absorption, anti-initial discoloration properties, thermal stability and bulk density of the vinyl chloride polymer obtained after the 8th-batch operation and the value of COD of polymerization effluent were measured in the same manner as in Example 1.
  • Polymerization was carried out in the same manner as in Example 1 except that the aqueous antioxidant dispersion A was replaced with an aqueous antioxidant dispersion B shown in Table 1 and the number of revolutions of the pump was changed to 350 rpm.
  • the aqueous antioxidant dispersion added to the polymerization mixture was in an amount of 1,050 g.
  • Polymerization was carried out in the same manner as in Example 1 except that the aqueous antioxidant dispersion A was replaced with an aqueous antioxidant dispersion C shown in Table 1 and the number of revolutions of the pump was changed to 200 rpm.
  • the aqueous antioxidant dispersion added to the polymerization mixture was in an amount of 600 g.
  • Antioxidant Dispersant or solvent Concentration of antioxidant (wt.%) Suspending agent Average particle diameter of antioxidant ( ⁇ m)
  • Antioxidant dispersion A 3,5-di-t-butyl-4-hydroxytoluene water 50 water-soluble partially saponified polyvinyl alcohol and hydroxypropyl methyl cellulose 4.1
  • Antioxidant dispersion B 3,5-di-t-butyl-4-hydroxytoluene methanol 20 - (uniform solution)
  • Antioxidant dispersion C triethylene glycol bis[3-(3-t-b utyl-5-methyl-4-hydroxyphenyl) propionate] acetone 35 - (uniform solution)
  • Example 1 Example 2 Comparative Example 1 Comparative Example 2
  • Example 1 Using as a reference a sample produced from the polymer obtained in Example 1, a sample having substantially the same anti-initial discoloration properties as the former sample was evaluated as "A"; a sample somewhat inferior thereto, as (B); and a sample greatly inferior thereto, as (C).
  • the sheetlike sample produced as the sample for measuring the anti-initial discoloration properties was put in a Geer oven maintained at a temperature of 185°C. The time taken until the sample blackened was measured.
  • COD in the polymerization effluent was measured by a method of measuring oxygen consumption ascribable to potassium permanganate (COD MN ) at 100°C as prescribed in JIS K0102.
  • the aqueous antioxidant dispersion can be added at a constant rate and stably, without causing any block-up of the interior of the pump even when the polymerization vessel is held at a high internal pressure.
  • vinyl chloride polymers having less uneven plasticizer absorption and having good anti-initial discoloration properties and thermal stability can be produced stably.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polymerisation Methods In General (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
EP00104108A 1999-04-09 2000-02-28 Procédé de production de polymère de chlorure de vinyl Withdrawn EP1043340A1 (fr)

Applications Claiming Priority (2)

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JP11102701A JP2000290308A (ja) 1999-04-09 1999-04-09 塩化ビニル系重合体の製造方法
JP10270199 1999-04-09

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7323505B2 (en) 2002-03-21 2008-01-29 Ciba Specialty Chemicals Corp. Aqueous dispersions for antioxidants
CN104514704A (zh) * 2013-10-01 2015-04-15 奈赤－泵和系统有限责任公司 用在钻孔中的潜水泵总成

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EP1394186B1 (fr) * 2002-08-19 2013-06-26 Shin-Etsu Chemical Co., Ltd. melange d'initiateurs pour la préparation de polychlorure de vinyle par polymérisation en suspension
US7184184B2 (en) * 2003-12-31 2007-02-27 Reliant Technologies, Inc. High speed, high efficiency optical pattern generator using rotating optical elements
US7125326B2 (en) * 2004-06-14 2006-10-24 Ebara Technologies Incorporated Apparatus and method for removing a CMP polishing pad from a platen
US8026403B2 (en) * 2007-06-27 2011-09-27 H R D Corporation System and process for production of liquid product from light gas
US7691953B2 (en) * 2007-06-27 2010-04-06 H R D Corporation System and process for production of polyvinyl chloride
US8394861B2 (en) 2007-06-27 2013-03-12 Hrd Corporation Gasification of carbonaceous materials and gas to liquid processes
US8133925B2 (en) * 2007-06-27 2012-03-13 H R D Corporation System and process for fischer-tropsch conversion
US20090061630A1 (en) * 2007-08-30 2009-03-05 Dupont Air Products Nanomaterials Llc Method for Chemical Mechanical Planarization of A Metal-containing Substrate
DE102010037440B4 (de) * 2010-09-09 2014-11-27 Seepex Gmbh Exzenterschneckenpumpe
CN104662712B (zh) * 2012-09-27 2017-04-12 丰田自动车株式会社 电极用糊的制造方法和二次电池

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60149608A (ja) * 1984-01-13 1985-08-07 Mitsui Toatsu Chem Inc 塩化ビニル類の重合方法
EP0281210A2 (fr) * 1987-03-06 1988-09-07 Shin-Etsu Chemical Co., Ltd. Procédé de préparation de polymères de chlorure de vinyle
EP0600696A1 (fr) * 1992-11-30 1994-06-08 Shin-Etsu Chemical Co., Ltd. Procédé pour préparer des polymères de chlorure de vinyle

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60149608A (ja) * 1984-01-13 1985-08-07 Mitsui Toatsu Chem Inc 塩化ビニル類の重合方法
EP0281210A2 (fr) * 1987-03-06 1988-09-07 Shin-Etsu Chemical Co., Ltd. Procédé de préparation de polymères de chlorure de vinyle
EP0600696A1 (fr) * 1992-11-30 1994-06-08 Shin-Etsu Chemical Co., Ltd. Procédé pour préparer des polymères de chlorure de vinyle

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
PATENT ABSTRACTS OF JAPAN vol. 009, no. 309 (C - 318) 5 December 1985 (1985-12-05) *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7323505B2 (en) 2002-03-21 2008-01-29 Ciba Specialty Chemicals Corp. Aqueous dispersions for antioxidants
EP1485441B2 (fr) † 2002-03-21 2009-08-05 Ciba Holding Inc. Dispersions aqueuses pour antioxydants
CN104514704A (zh) * 2013-10-01 2015-04-15 奈赤－泵和系统有限责任公司 用在钻孔中的潜水泵总成

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US6600000B1 (en) 2003-07-29

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